CN103738978B - A kind of clay prepares the method for NaX type zeolite molecular sieve pure phase - Google Patents
A kind of clay prepares the method for NaX type zeolite molecular sieve pure phase Download PDFInfo
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- CN103738978B CN103738978B CN201410013720.1A CN201410013720A CN103738978B CN 103738978 B CN103738978 B CN 103738978B CN 201410013720 A CN201410013720 A CN 201410013720A CN 103738978 B CN103738978 B CN 103738978B
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- clay
- molecular sieve
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- sio
- pure phase
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Abstract
The invention belongs to zeolite molecular sieve preparation method, relate to the method preparing NaX type zeolite molecular sieve pure phase with clay, be that the grog that clay becomes with sodium carbonate mixed calcining is uniformly mixed into colloid with sodium metaaluminate with water, then obtain NaX type zeolite molecular sieve pure phase through crystallization, filtration, washing, drying.Disposing mother liquor after filtration utilizes, as a part for raw material.Mother liquor of the present invention recycles, and reduces synthesis cost on the one hand, and first aspect no waste mine discharges, free from environmental pollution.The present invention has significant advantage, abundant raw material source in preparation cost, properties of product, technological process, environmental friendliness and economic profit etc., and with low cost, synthesize easy, equipment requirement is low, and properties of product are high, possesses industrial production potential.
Description
Technical field
The invention belongs to mineral process technology and field of zeolite molecular sieve preparation.Be specifically related to a kind of method that clay is Material synthesis NaX type zeolite molecular sieve.
Background technology
The preparation method of current artificial zeolite's molecular sieve take mainly chemical reagent as raw material, is synthesized by conventional hydrothermal method, although its synthetic technology is quite ripe, its cost is higher.Clay is the aggregate of common a kind of clay mineral, and main component comprises SiO
2, Al
2o
3, K
2o, Fe
2o
3with MgO etc., wherein SiO
2, Al
2o
3account for the overwhelming majority of content, it can waterglass in substituted chemistry raw material and sodium aluminate, greatly reduces cost, thus becomes the desirable synthesis material of zeolite molecular sieve.Clay is china natural resources Dominant mineral, and gross reserves is large, and cheap, current most clay is not exploited, and the part be only exploited is mainly used for calcining brickmaking, and the value of clay is not brought into play completely.NaX type molecular sieve is as a kind of high adsorption capacity, and the adsorbent of high selectivity, is widely used in the separation of various gas, purification and drying.Along with the expansion of industrial production demand, facilitate with the clay with low cost research for Material synthesis zeolite molecular sieve.At present about being that although the research of Material synthesis zeolite molecular sieve and report are many, not about the report with clay synthesis NaX type zeolite molecular sieve with cheap soil.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that clay prepares NaX zeolite molecular sieve, and its technical process is simple, can be promoted the comprehensive utilization ratio of clay by the method, increases economic benefit.Be that NaX type zeolite molecular sieve prepared by raw material with clay, the synthesis for NaX type zeolite molecular sieve provides a kind of cheap, the new raw material of abundance.
Technical scheme of the present invention is:
Prepare the method for NaX type zeolite molecular sieve pure phase with clay, it is characterized in that: have clay, sodium metaaluminate, sodium carbonate and water, according to SiO
2/ Al
2o
3=2 ~ 4.5, Na
2o/SiO
2=1.0 ~ 4.5, H
2o/Na
2the Ingredients Weight ratio relation of O=15 ~ 60, according to SiO in clay
2and Al
2o
3content, determines the ratio of required sodium metaaluminate, then determines the ratio of sodium carbonate; Mature calcined material under 650 DEG C ~ 900 DEG C temperature conditions is incorporated in by mixed to sodium carbonate and clay, add water successively in a kettle., sodium metaaluminate is uniformly mixed into colloidal with grog, be crystallization under the condition of 80 DEG C ~ 110 DEG C in temperature, refilter, wash, drying just prepares NaX zeolite molecular sieve pure phase.Preferably clay is pulverized by number, dries, sieves.Sodium carbonate and clay are mixed by a certain percentage, grinding evenly, calcine under uniform temperature, after cooling, by the grog grinding after calcining evenly, in stainless steel cauldron, add the grog after water, sodium metaaluminate and calcining by a certain percentage successively, sealing is placed in Constant Temp. Oven, crystallization a period of time at a certain temperature, through suction filtration, washing, drying, NaX zeolite molecular sieve pure phase can be prepared.By feed change proportioning, crystallization temperature and crystallization time, can regulate the degree of crystallinity of product.By first time, the NaX zeolitic solid product of synthesis carries out isolated by filtration, is then reclaimed by mother liquor, analyzes the content in mother liquor, then in later synthesis, reduces a certain amount of alkali when alkali melts, then supplements residue alkali number with mother liquor during crystallization.
Best-of-breed technology scheme of the present invention is:
Step 1: carry out XRF analysis to raw clay, determines SiO in raw material
2and Al
2o
3content, then after 100 object sieve screenings, drying 24 hours in the baking oven of 90 ~ 100 DEG C.
Step 2: by reaction raw materials according to SiO
2/ Al
2o
3=2 ~ 4.5, Na
2o/SiO
2=1.0 ~ 4.5, H
2o/Na
2o=15 ~ 60 are reacted.
Step 3: alkali melts process, mixes described clay according to aforementioned proportion with sodium carbonate, calcines under 650 DEG C ~ 900 DEG C temperature conditions, and calcination time is 1 ~ 4 hour, burnt grog is carried out grinding for subsequent use.
Step 4: Hydrothermal Synthesis process, by sodium metaaluminate, water and above-mentioned grog are uniformly mixed according to the above ratio, become colloidal, at room temperature stir aging 0.5 ~ 2.0 hour, are crystallization 4 ~ 20 hours under the condition of 80 DEG C ~ 110 DEG C afterwards in temperature.
Step 5: product is filtered, washs obtain NaX zeolite molecular sieve pure phase to pH=7 ~ 11, drying.
Step 6: the NaX zeolite molecular sieve solid product of synthesis carries out isolated by filtration by first time, then mother liquor is reclaimed, analyze the content in mother liquor, then in later synthesis, reduce a certain amount of alkali sodium carbonate when alkali melts, then supplement residue alkali number with mother liquor during crystallization.
The present invention utilizes clay to replace traditional industrial chemicals, and reduce the consumption of industrial chemicals, cost is low, utilizes alkali to melt clay, substantially increases the gel-forming property of clay, thus improves the utilization rate of clay.Technical process is simple, and practical, after crystallization, alkali lye can be recycled, and reduces the consumption of alkali.The present invention has significant advantage, abundant raw material source in preparation cost, properties of product, technological process, environmental friendliness and economic profit etc., and with low cost, synthesize easy, equipment requirement is low, and properties of product are high, possesses industrial production potential.
Detailed description of the invention:
Below in conjunction with technical scheme in detail specific embodiments of the invention are described in detail.
embodiment 1
(1) clay is pulverized, cross 100 mesh sieves.Drying 24 hours in the baking oven of 90 DEG C.
Its chemical composition is as follows through XRF results of elemental analyses:
| Chemical constituent | SiO 2 | Al 2O 3 | K 2O | Fe 2O 3 | TiO 2 | MgO |
| Percentage % | 60.87 | 15.24 | 13.80 | 7.01 | 1.24 | 0.78 |
(2) by reaction raw materials according to SiO
2/ Al
2o
3=2, Na
2o/SiO
2=1, H
2o/Na
2o=15 reacts.
(3) alkali melts process, is mixed by described clay with sodium carbonate according to aforementioned proportion, calcines under 650 DEG C of temperature conditions, and calcination time is 1 hour, burnt grog is carried out grinding for subsequent use.
(4) Hydrothermal Synthesis process, by sodium metaaluminate, water and above-mentioned grog are uniformly mixed according to the above ratio, become colloidal, at room temperature stir aging 0.5 hour, are crystallization 4 hours under the condition of 80 DEG C afterwards in temperature.
(5) filtered, wash obtain NaX zeolite molecular sieve pure phase to pH=7 ~ 11, drying by product, adopting National Standard Method (GB6287-86) to record the static saturation water adsorbance of this molecular sieve is 30%.
embodiment 2
(1) clay is pulverized, cross 100 mesh sieves.Drying 24 hours in the baking oven of 90 DEG C.
(2) by reaction raw materials according to SiO
2/ Al
2o
3=3, Na
2o/SiO
2=3, H
2o/Na
2o=45 reacts.
(3) alkali melts process, is mixed by described clay with sodium carbonate according to aforementioned proportion, calcines under 800 DEG C of temperature conditions, and calcination time is 2.5 hours, burnt grog is carried out grinding for subsequent use.
(4) Hydrothermal Synthesis process, by sodium metaaluminate, water and above-mentioned grog are uniformly mixed according to the above ratio, become colloidal, at room temperature stir aging 1 hour, are crystallization 10 hours under the condition of 95 DEG C afterwards in temperature.
(5) filtered, wash obtain NaX zeolite molecular sieve pure phase to pH=7 ~ 11, drying by product, adopting National Standard Method (GB6287-86) to record the static saturation water adsorbance of this molecular sieve is 34%.
embodiment 3
(1) clay is pulverized, cross 100 mesh sieves.Drying 24 hours in the baking oven of 90 DEG C.
(2) by reaction raw materials according to SiO
2/ Al
2o
3=4.5, Na
2o/SiO
2=4.5, H
2o/Na
2o=60 reacts.
(3) alkali melts process, is mixed by described clay with sodium carbonate according to aforementioned proportion, calcines under 900 DEG C of temperature conditions, and calcination time is 4 hours, burnt grog is carried out grinding for subsequent use.
(4) Hydrothermal Synthesis process, by sodium metaaluminate, water and above-mentioned grog are uniformly mixed according to the above ratio, become colloidal, at room temperature stir aging 2 hours, are crystallization 20 hours under the condition of 110 DEG C afterwards in temperature.
(5) filtered, wash obtain NaX zeolite molecular sieve pure phase to pH=7 ~ 11, drying by product, adopting National Standard Method (GB6287-86) to record the static saturation water adsorbance of this molecular sieve is 32%.
embodiment 4
By reaction raw materials according to SiO
2/ Al
2o
3=3, Na
2o/SiO
2=3, H
2o/Na
2o=45 obtains mother liquor after carrying out reaction preparation NaX zeolite molecular sieve pure phase, recording alkali content is 12%, in synthesis next time, reduce by the solid base sodium carbonate of 30% when alkali melts, supplement residue alkali number sodium carbonate when crystallization with mother liquor, after crystallization, filtration, washing, drying, obtain NaX zeolite molecular sieve pure phase.
embodiment 5
By reaction raw materials according to SiO
2/ Al
2o
3=2, Na
2o/SiO
2=1, H
2o/Na
2o=15 obtains mother liquor after carrying out reaction preparation NaX zeolite molecular sieve pure phase, recording alkali content is 14%, in synthesis next time, reduce by the solid base sodium carbonate of 40% when alkali melts, supplement residue alkali number sodium carbonate when crystallization with mother liquor, after crystallization, filtration, washing, drying, obtain NaX zeolite molecular sieve pure phase.
embodiment 6
By reaction raw materials according to SiO
2/ Al
2o
3=4.5, Na
2o/SiO
2=4.5, H
2o/Na
2o=60 obtains mother liquor after carrying out reaction preparation NaX zeolite molecular sieve pure phase, recording alkali content is 10%, in synthesis next time, reduce by the solid base sodium carbonate of 20% when alkali melts, supplement residue alkali number sodium carbonate when crystallization with mother liquor, after crystallization, filtration, washing, drying, obtain NaX zeolite molecular sieve pure phase.
embodiment 7
(1) pulverized by clay, its chemical composition is as follows through XRF results of elemental analyses:
| Chemical constituent | SiO 2 | Al 2O 3 | K 2O | Fe 2O 3 | TiO 2 | MgO |
| Percentage % | 60.87 | 15.24 | 13.80 | 7.01 | 1.24 | 0.78 |
(2) by reaction raw materials according to SiO
2/ Al
2o
3=2, Na
2o/SiO
2=1.0, H
2o/Na
2o=15 reacts, and determines the proportional quantities of required sodium metaaluminate, then determines the proportional quantities of sodium carbonate; Mature calcined material under 650 DEG C of temperature conditions is incorporated in by mixed to the sodium carbonate determined and clay, add water successively in a kettle., sodium metaaluminate is uniformly mixed into colloidal with grog, it is crystallization under the condition of 80 DEG C in temperature, again through suction filtration, wash to pH=9, NaX zeolite molecular sieve pure phase is just prepared in drying.
The mother liquor that the NaX zeolite molecular sieve suction filtration of above-mentioned synthesis obtains is reclaimed, analyzes the content in mother liquor, then in later synthesis, reduce the sodium carbonate of respective amount when alkali melts, then supplement remaining amount with mother liquor during crystallization.
embodiment 8
(1) clay is pulverized, cross 100 mesh sieves.Drying 24 hours in the baking oven of 90 DEG C.
(2) by reaction raw materials according to SiO
2/ Al
2o
3=4.5, Na
2o/SiO
2=4.5, H
2o/Na
2o=60 reacts
(3) alkali melts process, is mixed by described clay with sodium carbonate according to aforementioned proportion, calcines under 900 DEG C of temperature conditions, and calcination time is 4 hours, burnt grog is carried out grinding for subsequent use.
(4) Hydrothermal Synthesis process, by sodium metaaluminate, water and above-mentioned grog are uniformly mixed according to the above ratio, become colloidal, at room temperature stir aging 2.0 hours, are crystallization 20 hours under the condition of 110 DEG C afterwards in temperature.
(5) product is filtered, washs obtain NaX zeolite molecular sieve pure phase to pH=11, drying.
(6) the NaX zeolite molecular sieve solid product of first time synthesis is carried out isolated by filtration, then mother liquor is reclaimed, analyze the content in mother liquor, then in later synthesis, reduce the sodium carbonate of respective amount when alkali melts, then supplement remaining amount with mother liquor during crystallization.
Claims (2)
1. prepare a method for NaX type zeolite molecular sieve pure phase with clay, it is characterized in that: have clay, sodium metaaluminate, sodium carbonate and water, according to SiO
2/ Al
2o
3=2 ~ 4.5, Na
2o/SiO
2=1.0 ~ 4.5, H
2o/Na
2the Ingredients Weight ratio relation of O=15 ~ 60, according to SiO in clay
2and Al
2o
3content, determines the ratio of required sodium metaaluminate, then determines the ratio of sodium carbonate; Mature calcined material under 650 DEG C ~ 900 DEG C temperature conditions is incorporated in by mixed to sodium carbonate and clay, add water successively in a kettle., sodium metaaluminate is uniformly mixed into colloidal with grog, be crystallization under the condition of 80 DEG C ~ 110 DEG C in temperature, refilter, wash, drying just prepares NaX zeolite molecular sieve pure phase.
2. clay as claimed in claim 1 prepares the method for NaX type zeolite molecular sieve pure phase, it is characterized in that, raw clay used during preparation, formula rate and crystallization condition are as follows:
Step 1: carry out XRF analysis to raw clay, determines SiO in raw material
2and Al
2o
3content, then after 100 object sieve screenings, drying 24 hours in the baking oven of 90 ~ 100 DEG C;
Step 2: by reaction raw materials according to SiO
2/ Al
2o
3=2 ~ 4.5, Na
2o/SiO
2=1.0 ~ 4.5, H
2o/Na
2o=15 ~ 60 are reacted;
Step 3: alkali melts process, mixes described clay according to aforementioned proportion with sodium carbonate, calcines under 650 DEG C ~ 900 DEG C temperature conditions, and calcination time is 1 ~ 4 hour, burnt grog is carried out grinding for subsequent use;
Step 4: Hydrothermal Synthesis process, by sodium metaaluminate, water and above-mentioned grog are uniformly mixed according to the above ratio, become colloidal, at room temperature stir aging 0.5 ~ 2.0 hour, are crystallization 4 ~ 20 hours under the condition of 80 DEG C ~ 110 DEG C afterwards in temperature;
Step 5: product is filtered, washs obtain NaX zeolite molecular sieve pure phase to pH=7 ~ 11, drying;
Step 6: the NaX zeolite molecular sieve solid product of synthesis carries out isolated by filtration by first time, is then reclaimed by mother liquor, analyzes the content in mother liquor, in synthesis afterwards, reduces the sodium carbonate of respective amount when alkali melts, then supplements with mother liquor when crystallization.
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|---|---|---|---|
| CN201410013720.1A CN103738978B (en) | 2014-01-13 | 2014-01-13 | A kind of clay prepares the method for NaX type zeolite molecular sieve pure phase |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113480A (en) * | 1995-06-20 | 1995-12-20 | 北京新奇材料研究所 | Zeolite molecular sieve water purifying material and its manufacture |
| CN101817539A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Method for synthesizing A type molecular sieve by adopting attapulgite clay |
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2014
- 2014-01-13 CN CN201410013720.1A patent/CN103738978B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113480A (en) * | 1995-06-20 | 1995-12-20 | 北京新奇材料研究所 | Zeolite molecular sieve water purifying material and its manufacture |
| CN101817539A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Method for synthesizing A type molecular sieve by adopting attapulgite clay |
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